Method of thickening liquids and the products thereof



United States Patent Ofifice 3,417,018 METHOD OF THICKENlNG LIQUIDS AND THE PRODUCTS THEREOF Allan F. Burns, Whitehouse Station, N.J., assignor to Johns-Manville Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Dec. 18, 1963, Ser. No. 331,393

6 Claims. (Cl. 25213) This invention relates to a novel and unique viscosity control agent and method of employing same, and more particularly to the new use of a mineral material as a thickening and gelling agent.

Previous methods or techniques of thickening liquids or of producing viscid, relatively immobile or congealed liquid typically comprise the use of organic thickening or gelling means as exemplified by gums, starches, proteins, cellulose derivatives such as carboxymethylcellulose, etc. which modify fluid properties by regulating or increasing the surface or interfacial tension forces of a liquid phase. Other common techniques comprise simply the introduction of agents which effect a gel-like structure within the liquid medium including a variety of particulate filler materials exemplified by wood, flour, cork, carbon black, diatomaceous earth, silica gel and the like high surface area silicas, slate dust, sand and gravel, asbestos fibers, etc. which modify fluid flow characteristics by one or more mechanisms, as, for example, the subtraction of a portion of the liquid(s) and/or liquid constituent(s) by absorption and/or adsorption, the immobilization of the liquid or a phase thereof 'by adsorption or surface adhesion, or the structural interlocking of the particles to form a skeleton or relatively rigid body. Although adequately effective in many applications, such conventional means nevertheless frequently involve the utilization of comparatively costly materials or the addition of the agent in relatively high and adulterating proportions, or both, among other disadtages.

It is accordingly a primary object of this invention to provide a new and advantageous rheological use or application for a known mineral material.

It is also a primary object of this invention to provide a low cost mineral having unique and highly effective thickening or inspissating properties.

It is a further object of this invention to provide a new viscosity control agent which is not sensitive to moisture and provides a low cost and more eflective means of thickening and/ or gelling liquids.

It is a further object of this invention to provide an economical and effectual thickening or inspissating agent for polar liquids.

It is a still further object of this invention to provide an economical gelling agent for nonpolar liquids which is capable of thickening or immobilizing low viscosity nonpolar liquids to the point of gelling or congealing when applied in very minor amounts.

It is also an object of this invention to provide means of treating the mineral viscosity controlling agent of this invention to obtain optimum thickening and/or gelling properties therefrom.

It is also an object of this invention to provide a low cost material for the thickening and/or gelling of calking putties, sealants or fillers such as Wood fillers and putties, resin adhesives, flammable liquid fuels, asphaltic plastigels, greases, asphalts or asphalt products and the like materials.

These and other objects and advantages are more apparent from the hereinafter detailed description.

The present invention is founded in the discovery of the useful and advantageous thickening and/or gelling ing agent of this invention consists of a hydrous sodium-= magnesium silicate having the approximate composition' Na O.3MgO.6SiO .8H O. This material is pearly white fibrous mineral of semi-hard fibrous consistency and is fully described and identified by Fahey, Ross and Axelrod (1960), Lou-ghlinite, A New Hydrous Sodium Magnesium Silicate, The American Mineralogist, vol. 45, pages 270-281. Fahey et a1. assigned a refractive index value of 1.525 to this mineral whereas the loughlinite material utilized in the examples of this application exhibited a refractive index of 1504:0004. It was found,

however, that the refractive index of loughlinite was increased somewhat due to leaching or weathering of the mineral whereby it appears that the instant material may have been fresher than the sample examined by Fahey et al. For instance, the refractive index of a current sample of loughlinite was raised from 1.504 to 1.518 after four weeks of leaching with water. Nevertheless, the total water content 19.8% of the instant mineral compares very well with the Fahey et al figure of 20.5%.

The loughlinite mineral employedherein occurred as a cross veined fiber in small (maximum about 1 cm.) parallel and subparallel veins in a reddish fissile dolomitic shale along with several other well developed minerals of calcium and sodium. It was found that the crude loughlinite bearing ore was amenable to effective processing or refining by means of conventional asbestos milling and fiiberizing techniques or processes and apparatus, and in turn could be graded according to the Quebec standard for asbestos fibers. Thus employing conventional means, fibrous loughlinite is easily separated from the associated mother rock, fissile, =dolomitic shale, etc. Initial examinations indicated that the conventionally milled fiber contained a considerable amount, up to about 10% of organic material associated therewith but solvent extraction analysis established that the organic content was probably associated with the dolomitic shale rather than the fibrous loughlinite. Although this mineral resembles asbestos in appearance due to its fibrous structure and thereby could be refined or milled in a like manner, loughlinite has a few, if any, other analogous or common properties or characteristics with those of asbestos.

Typical chemical analyses of two distinct and representative samples of loughlinite are as set forth.

TABLE I.CHEMIO1IKII6 ANALYSIS OF THE MINERAL 3,417,018? Patented Dec. 17, 1968 5. Y

U GHLINITE Percent Sample A Sample B Moisture loss at; 0", 11.0 Ignition loss at 800 F...... 17. 9 7. 5 Additional loss at; 1,000 F. 3.8 0. 67 Additional loss at 1,800 F. 3. 7 Total ignition loss at 1,800 27. 0 22. 87 S102 40. 5 46. 3 l. 8 4. 8 2. 0

Further sundry properties of the mineral loughlinite air-jet milled loughlinite fiber whereby the efiiciency and comprise: uniformity of the gelling effect upon nonpolar liquids in- Particle shape-truly fibrous-like. creases with increased fiber opening. Without limiting this Specific gravity-2.2. invention to any theory it appears that the mechamsmof Optics-'y=1.504 and is parallel to fiber axis. this phase of the invention may be due to a combination Bulk densitybetween approximately 4.1 and 7.9. of the increased surface area amplifying possible chemical Surface area--5459 m. /gm. and/or physical surface interactions(s) with the liquid Water absorption240%. coupled with the greater number of individual fibers ef- Oil absorption-276%. fecting immobilization of a greater volume of liquid. F or Moisture content 105 C.-l6.4% on very pure handexample, 3% by weight of micropulverized loughlinite picked material. fiber effects a rather stiff gel in nonpolar hydrocarbons pH of aqueous slurryl0.7. such as car-hon tetrachloride and nonpolar aromatic hydrocarbons such as benzene, toluene, etc., but as the fiber is lFahey Ross and Axelmd supra opened even further as by air-jet milling a stiff gel of The unique and highly effective thickening and/ or gellcomparable rigidity can be obtained with only about 1 ing properties of the fibrous mineral loughlinite, in parto 2% by weight of fiber.

ticular the capacity to completely gel or solidify nonpolar As should be apparent from the foregoing, effective and liquids at relatively low concentrations, and the responappropriate proportions or concentrations of fibrous siveness of this mineral to relatively low cost available loughlinite to produce the desired degree of thickening asbestos milling and/or refining techniques provides an 2O and/or gelling are dependent upon both the particular agent or means of economically and effectively regulating liquid medium and/ or the fiber dimensions or conditions. or increasing viscosities of liquids to any desired degree For instance, 0.5 to 1 or 2% by weight of fiber may including substantial immobilization thereof. suffice for a particular application but in some cases 8 The loughlinite mineral material of this invention must to 10% by weight of fiber may be required with about 3 be fibrous in form or structure, its natural state, to effect to 5% by weight of loughlinite fiber imparting marked or impart any appreciable thickening and/or gelling at viscosity increases in most typical liquids and/or immorelatively low concentrations and reducing the natural bilizing gels in many nonpolar organic liquids. or initial fibers to a powder-like configuration as by grind- The following examples comprise specific illustrations ing or extensive milling results in a material which at low of the thickening or gelling properties and the capacity concentration merely settles out of a liquid phase with of the natural mineral loughlinite in a variety of diverse little over-all thickening effect and no trace of a gelling liquid media, and demonstrate the utility and pronounced etfect in nonpolar liquids such as benzene. Fiber dimenetfects of this material upon the rheological properties of sions for this application preferably average within the liquids. It should be understood that the techniques or range of 10 to 500 microns in length and 0.25 to 5 miprocesses, and conditions and results employed or given crons in diameter and for conventionally micropulverized are merely exemplary and are not to be construed as limitand air-jet milled loughlinite materials a typical fiber ing the invention to any particular data or conditions classifiication is as follows: recited therein.

TABLE IL-LOUGIILINITE FIBER DIMENSIONS Micropulverized Air-Jet Milled Approximate Fiber Length:

Maximum noted" 2,000 microns (2 700 microns.

Few greater than 1,000 microns (1 mm. 200 microns.

Majority 50-500 microns 10-100 microns.

Average 250 microns 50microns.

Approximate Fiber Diameter: Average 1 micron $6 micron.

When added to a highly polar liquid such as water, Certain of the hereinafter examples illustrating the proalcohol, etc., in apt quantities of, for example, about 2 nounced thickening and/or gelling properties of fibrous or 3% by weight thereof, the fibrous loughlinite produces loughlinite also comprise, when obtainable, viscosity data thick slurries of substantially greater consistency or thickfor asbestos fiber as a material or like fibrous form or conness than a slurry provided by an equal amount of asfiguration and similar composition for purposes of combestos or the like fibers of like dimensions. However, parison, and like data for bentointe clay or Bentone 38 when added to nonpolar organic liquids such as carbon as representative materials of typical commercial thicktetrachloride, benzene, toluene, xylene, etc., a gel is imeners of Wide application. To correlate the relative evaluamediately formed upon dispersion, and the more polar tion of loughlinite fiber with analogous materials, the conthe liquid medium the less gel-like and more slurry-like ventionally milled loughlinite having an average length of the mixture becomes. For example, only slurries are about A in. was compared with a grade 3T asbestos fiber formed when fibrous loughlinite is combined with liquids which is of approximately the same average length, and as polar as water, methanol, isopropanol and acetone. The the micropulverized loughlinite fiber was compared with slurries formed with polar liquids are quite light in color a grade 6D air cleaned and micropulverized asbestos fiber while the good gels produced from nonpolar liquids are of approximately like average length. The bentonite clay dark. Materials of intermediate polarity form mixtures comprised a standard commercial thickener for inorganic of intermediate consistency and color. This characteristic materials and the BENTONE 38, a product of Baroid Diof; loughlinite is in marked contrast to asbestos fiber which vision of National Lead (10., consists of an organic derivaforrns only slurries in nonpolar as well as polar liquid tive of a special magnesium montmorillonite designed for media. I thickening and gelling organic liquids.

In polar liquids the fiber length of the loughlinite ap- The viscosity data of these examples was obtained with pears to be a more significant factor than the fiber sura standard Brookfield viscometer with readings taken, face area in effecting viscosity increases, due apparently when possible, after 2, 4, 10 and 20 spindle revolutions. to a more stable fiber matrix or system as it is presumed, In [most cases the viscosity values dropped with time due based upon experimentations and observations, that the to orientation or alignment of the fibrous materials with thickening properties of loughlinite in polar media may the spindle or direction of rotation whereby only read he the result of mechanical fiber interaction. Although ings taken under the same conditions should be compared. crude loughlinite fiber gelled nonpolar liquids, the effi- The samples of the given compositions and concentraciency and uniformity of the gelling action thereof is tions thereof were tested in 400 milliliter quantities conmarkedly improved when the fibers are micropulverized, tained in 600 milliliter beakers under the conditions speciand optimum conditions can be achieved with the finer Th pi l e s given in each exam le except in the :runs on bentonite and'BENTONE 38 which, at the concentrations tested, provided suspensions so thin that the No. 1 spindle was utilized in all tests. All viscosity values are given in centipoises.

EXAMPLE I 6 ing testing and the micropulverized loughlinite did not; settle at any concentrations, whereas the asbestos fibers of comparable dimensions settled out in both instances prior to the completion of the tests.

EXAMPLE II The viscosity effect or thickening and gelling properties of conventionally milled loughlinite and a comparable dimensioned asbestos fiber, and micropulverized loughlinite also with a comparably sized asbestos, and BENTONE 38, an inorganic thickener for organic liquids, upon methyl- TABLE IIL-THICKENING EFFECT OF FIBROUS LOUGHLINITE AND RELATED MATERIALS UPON WATER Thickener, percent i 2 4 Spindle No 1 2 2 3 Thickener Revolu- Readings Viscosity Readings Viscosity Readings Viscosity Readings Viscosity tions Loughlinite fiber 2 0. 4 4 3. 6 144 ll. 2 448 13. 1 1, 310 4 0. 4 4 3. 5 140 9. 9 39G 11. 3 1, 130 0. 4 4 t 0. 0 396 9. 9 $190 0.4 4 9t 2 368 8 5 850 Asbestos fiber 2 0. 4 4 U) 4 0.4 4 U) (l (l 10 0. 4 4 0) (l t) 20 0.4 4 U) U) 0) Micropulverized loughlinite 2 0. 4 4 2. 8 112 17. l 684 81. 5 8, 150 4 0. 4 4 2. 4 96 15. 2 608 70. 9 7, 000 10 0. 4 4 2. 4 06 13. 8 552 61. 0 G, 100 20 0. 4 4 2. 3 92 12. 9 516 56v 7 5, G70

Mieropulverized asbestos 2 0. 4 4 1. 4 5G 3. 3 132 5. 4 540 4 4 4 t) 0) 5. 3 550 10 0. 4 4 5. 4 540 20 0. 4 4 U) Bentonite 2 t 0.4 4 0.5 5 0.6 6 1. G 16 4 0. 4 4 0. 5 5 0. 5 5 1. 8 18 10 0. 4 4 0. 5 5 0. 5 5 2. 2 22 20 0. 4 4 0. 4 4 0v 5 5 3. 4 34 l Settles out.

Only at the 1% concentration did the conventionally ethyl ketone were determined according to the conditions A milled loughlinite fiber exhibit any tendency to settle durand provided the results specified in Table IV.

TABLE IV.-THICKENING EFFECT OF FIBROUS Lonorg rg t 'ga AND RELATED MATERIALS UPON METIIYLETIIYL Thickener, percent 0 1 2 4 Spindle No 1 2 2 3 Thiekener Revolu- Readings Viscosity Readings Viscosity Readings Viscosity Readings Viscosity tions Loughlinite 2 0. 2 2 20. 7 823 9. 8 980 4 0. 2 2 19. 4 776 8. 6 860 10 0. 2 2 t) 17. 4 690 7. 7 20 0. 2 2 17. 2 688 8. 5 850 Asbestos fiber 2 0. 2 2 0) U) 0) 0) 4 0. 2 2 0) 0) 0) k) 10 0. 2 2 0) 0) a) 20 2 2 t) 0) 0) t) Mieropulverized loughlinite 2 0. 2 2 O) 9. 6 384 4 0. 2 2 3 372 0 2 2 20 0. 2 2 0) Micropulverized asbestos 2 0. 2 2 U) 4.0 400 4 0. 2 2 0) t) 10 0. 2 2 20 2 2 0) 0) 0) BENTONE 38 2 0.2 2 0.7 7 0.8 8 1.1 11 4. o. 2 2 0) 10 0. 2 2 t) t) 20 0. 2 2 0) l Settles out.

1 Thick slurry-like gel formed; good readings not possible.

As is apparent, the asbetos settled out or exhibited a tendency to settle out under all concentrations examined as did the BENTONE 38 whereas the loughlinite produced a marked viscosity increase at 2% concentration and at 4% produced a viscid gel in which there was no ding at 4% flow and could not be utilized to obtain a reading.

EXAMPLE IV Glass fibers have been disclosed in the prior art as having viscosity imparted properties whereby the relative thickening and/or gelling effects of glass fiber and fibrous rmined under the loughlinite were compared in a N0. 40 motor oil with a ith the effects comprising the data of Brookfield viscometer under the same conditions as the foregoing examples. The glass fibers employed had a Readings Viscosity Readings Viscosity Readings Viscosity Readings Viscosity In these runs the asbestos fiber of both size classifications settled out before any significant readings could be obtained whereas the fibrous loughlinite in each case increased the viscosity at the higher concenrized material produced a concentration.

EXAMPLE III In this example the efiect of micropulverized loughlinite I 0 size asbestos fiber and BENTONE 38 TABLE V.THICKENING EFFECT OF FIBROUS LOUGI-ILlNlTE AND RELATED MATERIALS UPON BENZENE Thickener Revolutions markedly trations, and the micropulve thick slurry-like gel too viscous to obtain a rea and a comparable upon the viscosity of benzene was dete conditions and w Table V.

Thickener, pcreent Spindle No.

S J a t L .1 m m m 0.000 mmm 0 m I m m m m 0 ((l\( e 0 v 1 1 1 1 1 1 v 1 w W R $53 221% 63 2 t Y m S O 4 7 0 o H T 1 s t U 0 g 3 63 8 ma M .m 1786 4 220 6966 d 0000 05 7mm 1 000 r 0. w NIBH 654.4. 1000 a m o R T N y t O n m a mama mama mmmz 03000 00 7 .1 S w 4179 1953 2 84. \1)\/ 1,, 1,, 1.1.. %%mM 000 /8 L .m w 444 8222 o R 1 t E me & M m 6348 834 8 04 12 d 5. 3 1/ u m aim mm m 8116 mm (l( 0000 V. i R a n I. E a T v. 1 t n A 000% 0 00 0 0 e 026 b m m w 1943 amen ammm .0).\./ n1))) 5)) i s vvi, 1', .b ("U00 0W0 m R 44 44 M 1111 1111 W. D 1 4 m .m c a s N m m a h w A n s T n f. E .1 5 6 5 1 9 1558 I w T M 4 21 m 7787 K 7&&7 E i .\..ID)n/n/ 5\)\)\/ n1 1 C 2 22 .1 ((K( 000 :0. N R W h I a y M... a I. t O .m G 2222 L 8888 F 2 U 0 7777 d 6666 S Lb Modal 0 1220 29.9-9- L w m m m 0 2 w w u o m w R .m 33 U 2222 1231 e m m aaaa i 9903 e9 9 3222 2222 2222 m F e M 0000 00 0 0 0 0 0 0 F R m. 0 n n m m n m m m 0 m E m m m Wm 24m% 24 24N% 4 0 2 0 2400 g F 1m 12 12 .m m u u 0 R m o N m n n u e h N a u m n u n a n rm I N u u n n n n n g N n u n u n E .1 n K n n n n m m n w G n n n n u n I .m w H m n 0 u n n u n 1 t mu d T n u u u b u e n n n n m m n m 1 u m n n u u m d lmw n n H u a m a ma w t. n u m m o r a D as B m n w o 0 v v N 1d m o o M M 1m 1 0 M 8 N M T T D. e U M M O 0 SQ l 0 0 0 r r. N 12 H d A A. 4 .w .m E b .m D. M .1 B i 0 0 0 B F S R N N N 9 EXAMPLE v To ascertain the extent of the thickening and/ or gelling efiects of fibrous mineral loughlinite this material was applied in minor amounts to a variety of common organic liquids of varied composition and/or organic categories. The water and organic liquids and/or liquid compositions utilized, and the concentrations of the fibrous material together with the observed results of admixing these materials are tabulated as follows:

TABLE VIL-THICKENING AND/OR GELLING EFFECT OF FIBROUS LOUGHLINI'IE UPON VARIOUS LIQUIDS Liquid Fibrous Loughlinite Eflect Water 4% micropulverized Thick slurry.

Do 4% fiber lz to in. 'lhickened. B 2 yair jet milltfiLd enzene airjet mi e Toluene 3% micropulverize i Xylene 3% air jet milled gel Carbon Tetrachloride 4% niicropulvcrized. tftiiihs'iiets e ye y e ne Methyl Alcohol" 4% micropulveiizcd Thick slurry. Isopropyl Alcohol Heptane 3% m1cropulverized Gel-like.

Kerosene r .do Solid gel.

SAE No. 40 Oil 4% fiber bz to in. Very viscous, slow flow.

air jet milled. I

SAE No. 40 Oil.- 4% micropulverized Viscous fluid.

Z. air jet milled Commander H Oil 6% micropulverize 0. Solid gel.

Thick grease with no flow.

JP-l (jet fuel)-.. 2% air jet milled ..I

Do 3% niicropulverized I 0. JP4 (jet fuel) 2% air jet milled Gel-like.

A paratfino oil comparable in viscosity to S.A.E. No. 40 motor oil.

EXAMPLE VI A specific application of the thickening effect of fibrous mineral loughlinite comprises its use in calking putties and the like sealing compounds. Accordingly, the thickening and/or gelling properties of this mineral were compared with a standard commercial multipurpose thixotropic agent for non-aqueous media, Thixcin, a product of Baker Castor Oil Co. consisting of a finely divided, solidified vegetableoil derivative, in the vehicle or liquid phase, without the filler solids, of a typical caiking putty formulation comprising 49.3 grams of soybean oil, 4.8 grams of fatty vegetable acid 21.9 grams of low molecular weight polybutene, and 24.0 grams of mineral spirits. In this medium, 1% by weight of air-jet milled fibrous loughlinite produced a degree of thickening equivalent to 5% by weight of the Thixcin, a thick but pourable liquid, and at 3% by weight concentration the air-jet milled fibrous loughlinite effected a gel which barely flowed and at 5% concentration the gel would not fiow.

EXAMPLE VII Fibrous mineral loughlinite was employed as a thickening and/or gelling agent in a typical asphaltic plastigel sealing compound of the composition:

Grams Commander H oil 310 Milled loughlinite Pulverized gilsonite 240 No. 50 Blue black slate dust 240 1 The fatty vegetable acid had a saponlfication value of 198 to 207, an iodine number of 115 to 124, and an acid number of 195 to 205.

of at least about 0.5% up to about 10% of said fibrous loughlinite based upon the weight of said organic liquid base.

4. A composition comprising a polar liquid base thickened with fibrous loughlinite in an effective amount of at least about 0.5% up to about 10% of said fibrous loughlinite based upon the weight of said polar liquid base.

5. A composition comprising a non-polar liquid base thickened with fibrous loughlinite in an effective amount of at least about 0.5% up to about 10% of said fibrous loughlinite based upon the weight of said non-polar liquid base.

6. A composition comprising aliquid base thickened with fibrous mineral loughlinite in an effective amount of at least approximately 0.5% up to approximately 10% by weight of said fibrous mineral loughlinite based upon j the weight of said liquid base, said fibrous mineral loughlinite having an average fiber particle size within the range of about 10 to about 500 microns in length and about 0.25 to about 5 microns in diameter.

References Cited UNITED STATES PATENTS OTHER REFERENCES Manufacture and Application of Lubricating Grease, by Boner, Reinhold Pub. Corp., New York, 1954, page 701.

DANIEL E. WYMAN, Primary Examiner.

IRVING VAUGHN, Assistant Examiner.

US. Cl. X.R. 

1. A COMPOSITON COMPRISING A LIQUID BASE THICKENED WITH FIBROUS LOUGHLINITE IN AN EFFECTIVE AMOUNT OF AT LEAST ABOUT 0.5% BY WEIGHT OF SAID FIBROUS LOUGHLINITE BASED UPON THE WEIGHT OF SAID LIQUID BASE. 